Monoazo dyestuffs



Patented Sept. 11, 1945 UNITED STATES PATENT OFFICE MONOAZO DYE STUFF SArthur Howard Knight and William Elliot Stephen, Blackley, England,assignors to Imperial Chemical Industries Limited, a corporation ofGreat Britain No Drawing. Application December 22, 1942, Se-

rial No. 469,845. In Great Britain December 29,

1 Claim.

tuted by methyl, methoxy, or sulphonic groups or other simple azodyestuff substituents, X stands for mono-chloro or -bromo-alkyl (C1 toC3), Y stands for hydrogen, alkyl (C1 to C6), aralykyl, cycloalkyl,alkoxy-alkyl, or aryl, and coupling with a2-acylamino-8-naphthol-6-sulphonic acid, in which the acyl group isformyl, alkoxyformyl, succinyl (i. e., B-carboxypropionyl) benzoyl,arylsulphonyl, hydroaromatic sulphonyl, hydroaromatic carbonyl,aralkoxy-A, cycloalkoXy-A, aryloxy-A or alkoxy (C1 to C4)-A (Arepresentin acetyl, propionyl or butyryl), said cyclic acyl 4-amino- 1-N-ethyl-omega-bromoacetanilide 4-amino- 1-N-benzyl-omega-chloroacetanilide4-aminol-N-cyclohexyl-omega-chloroacetanilide5-amino-2-N-cyclohexyl-omega-chloroacettoluidide 3 -amino-1-N-benzy1-omega-chloroacetanilide4-amino-2-N-benzyl-omega-chloroacet-toluidide 4-amino-1-N-phenyl-omega-chloroacetanilide 4-amino- 1 -N-cyclohexyl-omegachloropropionanilide V 4-amino- 1-N-cycloheXyl-omega-bromopropionanilide 4-amino- 1-N-cyc1ohexyl-a-bromopropionanilide -amino-l-N-cyclohexyl-omega-bromo-acetgroups optionally bearing nuclear substituents,

for example methyl or halogen, and the remaining hydrogen of the aminogroup may be replaced by alkyl, hydroxyalkyl or aryl.

Also according to the invention we use the dyestufis in colouring animalfibres, e. g., wool and anilide4-amino-2-N-benZyl-omega-chloroacetanisidide4-amino-l-N-cyclohexy1-omega-chloroacetanilide-2-su1phonic acid3-amino-l-N-benzyl-omega-chloropropionanilide (obtainable by methodsdescribed in British Patent 544,409 (or our U. S. Patent No. 2,346,492),a-amino-l-N {3 ethoxyethyl-omega-chloroacet anilide (obtainable byacetylating N-fi-ethoxyethylaniline, nitrating removing the acetyl groupby hydrolysing, causing the resulting 4-nitro-1- N-p-ethoxyethylanilineto react with chloroacetyl chloride and reducing), and4-amino-1-N-cyclohexyl-omega chloroacetanilide-2-sulph0nic acid(obtainable by chloroacetylating sodiuml-nitrol-N-cyclohexylaniline-Z-sulphonate and reduc ing).

Derivatives of 2-amino-8-naphthol-6-sulphonic acid, or, as it may bemore briefly termed, gamma acid, which may be used, for example, inaccordance with the invention, are listed below. They are obtainable byinteraction between gamma acid, or the appropriate N-alkyl,-hydroxyalky1 or -aryl derivatives thereof, and the necessary acidchloride or anhydride. For instance, N-o-chloro phenoxyacetyl-gamma acidmay be made by interaction between gamma acid and o-chlorophenoxyacetylchloride (got by the action of thionyl chloride ono-chlorophen'oxyacetic acid) N-cyclohexyloxyacetyl-gamma acid can bemade by interaction between gamma acid and cyclohexyloxyacetyl chloride(produced by the action or" thionyl chloride on cyclohexyloxyaceticacid, the manufacture of which acid is referred to in British Patent413,728); N-methoxyacetyl-N- phenyl-gamma acid may be obtained byinteraction between N-phenyl-gamma acid and the anhydride or chloride ofmethoxyacetic acid.

N-methoxyacetylgamma acid N-ethoXyacetyl-gamma acidN-n-butoxyacetyl-gamma acid N-a-methoxypropionyl-gamma acidN-a-methoxy-n-butyryl-gamma acid N-v-ethoxy-n-butyryl-gamma acidN-phenoXyacetyl-gamma acid N-c-chlorophenoxyacetyl-gamma acidN-p-chlorophenoxyacetyl-gamma acid N-p-methylphenoxyacetyl-gamma acidN--chloro-Z-methylphenoxyacetyl-gamma acid N-tetrahydronaphthalone-2sulphonyl gamma acid N-formyl-N-phenyl-gamma acidN-hexahydrobenzoyl-gamma acid The new dyestuffs of the present inventiondye wool from an acid bath and yield, in general, various shades of redor reddish brown, the dyeings being characterised by very good fastnessto severe washing and milling, and good fastness to light.

The invention is illustrated, but not limited, by the following examplesin which the parts are by weight.

Example 1 2125 parts of -amino-l-N-ethyl-omega-chloroacetanilide aredissolved in a mixture of 300 parts of water and parts of 36%hydrochloric acid. 6.9 parts of sodium nitrite in 50 parts of water areadded. The diazonium solution so-obtained, after cooling to 5-10 C., isadded to a stirred and cooled mixture of 33.3 parts of sodiumZ-(methoxyacetyD-aminc 8-naphthol-6- sulphonate, 600 parts of water and21 parts of anhydrous sodium carbonate. The mixture is stirred untilcoupling is complete. 250 parts of sodium chloride are added toprecipitate the dyestufl which is then filtered off, washed with 20%sodium chloride solution, and dried. I

The new dyestufi is red, dissolvin in water with a scarlet-red colourand in concentrated sulphuric acid with a red colour. It dyes wool froma dyebath containing sulphuric acid and Glaubers salt in scarlet-redshades, the dyeings having very good fas-tness to severe washing,

milling and perspiration, and good fastness to light.

The above coupling can also be carried out in the presence of other mildacid-binding agents such as sodium bicarbonate or sodium acetate.

Example 2 22.6 parts of 4-amino-2-N-ethyl-omega-chloroacet-toluidide aredissolved in a mixture of 400 parts of water and 25 parts of 36%hydrochloric acid. After cooling to 5+10 C., there are added 6.9 partsof sodium nitrite in 50 parts of water. The solution of the diazoniumcompound so-obtained is added with stirring to a cooled mixture of 33.3parts of sodium Z-methoxyacetyl-amino- -S-naphthol-G-sulphonate, 600parts of Water, 21

par-ts of anhydrous sodium carbonate and parts of sodium chloride.Coupling is rapid and, when complete, a further parts of sodium chlorideare added and the precipitated dyestuff filtered oii, washed withsaturated sodium chloride solution and dried.

The new dyestufi is red-brown, dissolving in Water with a scarlet-redcolour and in concentrated sulphuric acid with a red colour. It dyeswool from an acid dyebath in bright scarlet-red shades, the dyeingshaving very good fastness to severe washing and milling, and goodfastness to light.

Example 3 26.25 parts of 4-amino-l-N-cyclohexyl-omegachloroacetanilideare dissolved in a mixture of 350 parts of water and 25 parts of 36%hydrochloric acid and diazotised at 1530 C., by the addition of '7 partsof sodium nitrite. The resulting diazonium solution, after filtration ifnecessary, is cooled. to 5-10 C., and added to a cooled and stirredsolution of 33.3 parts of sodium 2- (methoxyacetyl) -amino-8-naphthol 6sulphonate in 550 parts of Water to which have been added 21 parts ofanhydrous sodium carbonate. When coupling is complete the dyestuff isfiltered off and dried. It is yellowish red, dissolving in water with ayellowish scarlet colour and in concentrated sulphuric acid with abluish red colour.

The new dyestuff dyes wool from a dyebath containing sulphuric acid andGlaubers salt in bright scarlet-red shades, the dyeings having very goodfastness to severe washing, and milling, and good fastness to light.

Example 4 To a solution of 28.65 parts of sodium 3-aminoomegachloroacetanilide 4 sulphonate in 450 par-ts of water there are added 35parts of 36% hydrochloric acid followed by 6.9 parts of sodium Example 521.25 parts of l-amino-l-N-ethyl-omega-chloroacetanilide are diazotisedas in Example 1. The diazonium solution so-obtained is gradually addedto a solution at 10-12 C. of 40 parts of sodium2-phenoxyacety1amino-8-naphthol-6-sul phonate in 800 parts of watercontaining 28 parts of crystalline sodium acetate. When coupling iscomplete the dyestufi is filtered off, washed'with aqueous sodiumchloride, and dried.

The new dyestufi dyes wool from a' dyebath containing sulphuric acid andGlau-bers salt in scarlet shades, the dyeing having good fastness tosevere washing, milling and light.

Example d 22.65 parts of 4-amino-Z-N-ethyl-omega-chloroacet-toluidideare diazotised as in Example 2. The diazonium solution so-obtained isadded to a stirred solution of 41 parts of sodiumZ-benzyloxyacetylamino-B-naphthol-6-sulphonate in 800 parts of watercontaining 28 parts of crystalline sodium acetate. When coupling iscomplete, 70

parts of sodium chloride are added to precipitate the dyestufi, which isthen'filtered off, washed with 5% aqueous sodium chloride and dried.

The new dyestuff dyes wool from an acid bath in bright scarlet shades,the dyeings having very good fastness to severe washing and milling andgood fastness to light.

E :rample 5055 C. The coagulated dyestuff is then filtered off, washedwith aqueous sodium chloride and dried.

The new dyestuff dyes wool from a dyebath containing sulphuric acid andGlaubers salt in dull scarlet shades, the dyeings having good fastnessto severe washing, milling and light.

If, instead of the 4arnino- 2-N-ethyl-omega bromopropiontoluidide usedabove there are employed 22.65 parts of 4-amino-l-N-ethyl-omega-.chloropropionanilide, a dyestufi is obtained which dyes wool insomewhat reddershades', the dyeings having similar fastness properties,whilst the use 'of 22.65 parts of 4-amino-1-N is0-pr0py1-omega-chloroacetanilide as diazo component results in 'a dyestufl"givingyellowishred shades on wool, the dyeings having very good fastnessto severe washing and milling and good fastness to light.

.Eguamlple 8 22.65 parts of4-amino-2-N-ethyl-omega-chloroacet-toluidideare diazotised as in Example 2'. The solution of the diazo compound isthen added to a solution of 34.7 parts of sodium 2-(N-methoxyacet'yl Nmethyl) -amino-8-naphthol-6- sulphonate in 400 parts of water containingexcess of sodium acetate. When coupling is. complete 120 parts of sodiumchloride are added to precipitate the dyestufl which is thenfilteredoff, washed with aqueous sodium chloride and dried.

The new dyestuff dyes wool from an acid bath in red-brown shades,thedyeings having very good fastness to severe washing and milling andgood fastness to light.

If, instead of 34.7 parts of sodium 2-(N-me- Bit thoxyacetyl -N methyl)-amino-8-naphthol-6- sulphonate there are employed 37.7 parts of sodium2 (N methoxy-acetyl-N-c-hydroxyethyl) amino-8-naphthol-6-su1phonate, adyestufi is ob tained having similar properties.

Example 9 g 2 7.45 parts of 3-amino 1 N-benzyl-omegachloroacetanilideare dissolved in 400 parts of water'and 25parts of 36% hydrochloricacid. Six and nine-tenths parts of sodium nitrite are added. Thediazonium solution so -obtained, after filtration if necessary, is addedto a'stirred solution at 10-12 C. of 43 parts of sodium 2-( 2'-chlorophenoxyacetyl) amino-8-naphthol-6-sulphonate in 600 parts of watercontaining 28 parts of crystalline sodium acetate. When coupling iscomplete the precipitated dyestufi is filtered off, washedwith 5%aqueous sodium chloride and dried.

' The new dyestufl dyes W001 from an acid bath in scarlet shades, thedyeings havingvery good fastness to severe washing and milling and goodfastness to light. v

Example 10 21.25 parts of 4amino-l N-ethyl-omega-chloroacetanilide aredissolved in a, mixture of 300 parts of water and 25 parts of 36%hydrochloric acid. 6.9 parts of sodium nitrite are added. The diazoniumsolution so-obtained' is cooled to 5-10 C. and added to a cooled andstirred mix ture of 86.5 parts of sodium 2-benzoylamino-8-naph'thol-G-sulphonate, 450 parts'of water, 21

parts of anhydrous sodium carbonate and Exam le 11 The above example iscarried out, the 21 parts of anhydrous sodium carbonate being replacedby 28 parts of crystalline sodium acetate. A dyestuff is obtainedwhich-dyes woolfrom a dyebath containing sulphuricacid and Glaubers saltin somewhat yellower and'brighter shades of scarlet,

th'e dyeings having similar fastness properties.

' Example 12 22.6 parts of 4-amino-l-N-ethyl-omega-chloropropionanilideare employed in place of the 4- amino-1-N-ethyl-omega-chloroacetanilidein Example 11. A new dyestufi is obtained which dyes wool, from an acidbath in scarlet-red shades of good fastness to severe washing, millingand light.

Example 13 22.65 parts of 4-amino-l-N-ethyl-omega-chloropropionanilideare dissolved in 300 parts of water and 25 parts of 36% hydrochloricacid and diazotised by the addition of 6.9 parts of sodium nitrite. Thediazonium solutionis stirred into a solutionat 5-10 C; of 38 parts ofsodium 2- N-benzoyl N methyl-amind-S-naphthol-6-sulphonate in 600 partsof water containing 21 parts of anhydrous sodium. carbonate. Whencoupling is complete, 60 parts of 'sodium chloride are added and. thedyestuff filtered off washed with aqueous sodium chloride and'dried. Itdyes wool from a dyebath containing sulphuric acid and Glaubers salt inreddish brown shades, the dyeings having good fastness to severewashing, milling and light. v

If in the above example an equivalent amount of sodium2-N-benzoyl-N-ethyl-amino-B-naphthol-fi-sulphonate or of2-N-(2"-chlorobenzoyl)- N -methyl amino 8 naphthol-fi-sulphonate is usedin place of the sodium 2-N-benzoyl-N-methylamino 8naphthoI-G-sulphonate, a dyestuff having similar properties is obtained.

Y Example 14 26.65 parts of -amino-l-N-cyclohexyl-omegachloroacetanilideare dissolved in a mixture of 350 parts of warm water and 25 parts of36% hydrochloric acid. The solution, is cooled to 15-30 C. and asolution of 6.9 parts of sodium nitrite in 50 parts of water added. Thediazonium solution so-obtained is filtered, if necessary, and aftercooling to5-10 C. is gradually stirred into a similarly cooled solutionof 33.3 parts of sodium 2-ethoxyformyl-amino 8 naphthol-6- sulphonate in650 parts of water containing 28 parts of crystalline sodium acetate.-:When cou pling is complete, the dyestuff is filtered ofi, washedwith 5%aqueous sodium chloride and dried, v v

The new dyestuff dyes wool from a dyebath containing sulphuric acid andGlaubers saltin yellowish red shades, the dyeingshaving very goodfastnessto severe washing and milling and good fastn'ess to light.

'If, inplace of the 33.3 parts'of sodium 2,-ethoxy-formyl-amino-8-naphthol '6 sulphonate there are used 38 parts ofsodium 2-N-benz'oyl- N-methyla-mino8-naphthol-6-sulphonate or 36.5 partsof sodium 2-N-formyleN-phenyl-amino-8- naphthol-G-sulphonate, dyestuffs.are. obtained which yield on wool reddish brown shades of goodfas-tness properties.

V lilznmnple 15 22.6 parts of 4-amino-2-N-ethyl-omega-chloroacet-toluidide are dissolved'in 400 parts of water and25 parts of 36% hydrochloricacid, and diazotised at 5-10 C. bytheaddition of 6.9 parts of. sodium nitrite. The diazonium solution isadded to a cooled and stirred mixture of 40.9 parts of-sodiumZ-N-benzoyl-N-,3hydroxyethyl amino-8-naphthol-6-sulphonate, in 400 partsof Water and 21 parts of anhydroussodium carbonate. Coupling is rapidand, when complete, the dyestuff is precipitated by addition of 50 partsof sodium chloride, filtered ofi and dried.

The new dyestuif dyes wool irom an acid dyebath in reddish brown shadesof very good fastnessto severe washing andmilling andgoodfastnesstoliglit. A A dyestuff'having similar properties is obtainedif 2-N-benzoyl-N- -hydroXyethyl-amino8-naphthol-6-sulphonate used aboveis replaced by the equivalent amount ofsodium2-N-benzoyl-N-yhydroxy-propylamino-8-naphthol-6-sulphonate.

.Erample 16 26 parts of 4-amino-l-N-phenyl-omega-chloroacetanilide aredissolved in 400 parts of water and 25 parts of 36% hydrochloric acidand diazotised by the addition of 6.9 parts of sodium nitrite. Thefiltered diazonium solution is stirred into'an aqueous solution at 5-10C. of 38.3 parts of disodium.2-succinylamino-8-naphtholfi-sulphonatecontaining an excess of sodiumacetate. The azo dyestufi thrown down is filtered off, washedwith 10%aqueous sodium chloride anddried.

The newv dyestuff dyes wool from a dyebath containing sulphuric acid andGlaubers salt in red-brown shades, the dyeings having very good iastnessto severe washing and milling.

Example 17 22.65 parts of 4-a-mino-l-N-isopropyl-omegachloro-acetanilideare dissolved in 300 parts of water and 25 parts of 36% hydrochloricacid. 6.9 parts of sodium nitrite are added. The diazonium solution soobtained is gradually stirred into a mixture at.510 C. of 41.5 parts ofsodium 2-(p-toluenesulphonyl) -amino-8 naphthol 6 sulphonate, 500 partsof water and 28 parts of crystalline sodium acetate. When coupling iscomplete the dyestuff is filtered ofi, washed with 5% aqueous sodiumchloride and dried.

The new dyestufi dyes wool from an acid dyebath in scarlet shades, thedyeings having very good iastness to severe washing and good fastness tolight.

A dyestuff having very similar properties is obtained if 24 parts of4-amino-l-N-secbutylomega-chloro-acetanilide are used instead of the-amino-l-N-isopropyl-omega chloroacetanilide employed above.

Example 18 To 25.65 parts of4-amino-l-N-fi-ethoxyethylomega-chloroacetanilide dissolved in 300 partsof, Water and 25 parts of 36% hydrochloric acid, 6.9 parts of sodiumnitrite are added. The diazonium solution is stirred into a mixture of36.5 parts of sodium 2-benzoylamino-8-naphthol-6-sulphonate, 600 partsof water and 28 parts of crystalline sodium acetate. When coupling iscomplete par-ts of sodium chloride areadded to pre: cipitate thedyestuff which is then filtered ofi. Washed with 10% aqueoussodiumchloride and dried. I

The new dyestuff dyes Wool from an acid bath in red shades, the dyeingshaving good fastness to severe washing, milling and light.

The corresponding dyestuff madefrom 24.25

parts of. 4-amino-1-N-[3 methoxyethyl omega chloroacet-anilide in placeof the 4-amino-1-N- B ethoxyethyl omega chloroacetanilide used above,yields reddyeings on-wool of similar fastness properties.

e Example 19 A solution of 27.45 parts of 3-amino-l-N-benzyl-omega-chloroacetanilide in 400 parts of water and 25 parts of 36%hydrochloric acid is diazotised by the addition of 6.9 parts of sodiumnitrite. The, resulting diazonium solution is filtered if necessary andstirred into a solution at 5-l0 C. of 38.3 parts of disodiumz-succinylamino ii-naphthol-6-sulphonate in 500 parts of watercontaining excess of sodium bicarbonate. The azo dyestuff isprecipitated by the addition of sodium chloride, filtered off and dried.It dyes wool from an acid bath in yellowish red shades, the dyeingshaving good fastness to severe washing, milling and light.

- The invention is further illustrated by the examples listed in thefollowing table, wherein the shorter designation gamma acid has beenused for 2-amino-8-napthol-6-sulphonic acid.

Diazo component Coupling component Shade on wool3-amino-omega-chloroacetanilideA-sulphonic acid-4-amino-1-N-ethyI-omega-chloroacetani1ide4-amino-1-N-n-butyl-omega-chloroacetanilide do N-benzoyl-N-methyl-gammaacid WILLIAM ELLIOT STEPHEN.

4-amino-1-N-cyclohexyl-omega-chloropropionanilide. D0.4-amino-1-N-ethyl-omega-chloroacetanilide N-ethoxyformyI-N-ethyl-gammaacid. Dull scarlet. 4-amino-2-N-ethyl-omega-bromopropiontoluidideN-ethoxyformyl-gamma acid Yellowish red.4-amino-2-N-ethyl-a-bromopropiontoluidide N-methoxyformyl-gamma acid Do.4-amino-1-N -isopropyl-omega-chloroacetanilideN-tctrahydronaphthalene-Z-sulphonyl-gamma ac1d Red. doN-hexahydrobenzoyl-gamma acid Do.

4-amino-1-N-cyclohexyl-omega-chloropropionanilide.N-2ch1or0benzoy1-gamma acid.v .,do N-(S-bromobenzoyl-gamma acid Red.

4-amino-2-N-benzyl-omega-chloroacet-toluidide N-ethoxyformyl-gamma aeid.Yellowish red. 4-amino-omega-chIoroaoetanilide-B;su1phonic acidN-benzoyl-N-methyl-gamma acid Reddish brown.

We claim: 15 The monazo dyestufi which in the form of Its acid isrepresented by the formula (|)H C1CH2- |1-N-C =N 47145-01120 0118 20 (I)I H 038 H 0 ARTHUR HOWARD KNIGHT.

